Olefinic phosphate triesters and process for making same



musician Unite 3,079,417 OLEFINIC PHOSPHATE TRIESTERS AND PROCESS FORMAKING SAME Martin W. Farrar, Webster Groves, Mo., assignor to MonsantoChemical Company, St. Louis, Mo., a corporation of Delaware No Drawing.Filed Oct. 29, 1959, Ser. No; 849,461 17 Claims. (Cl. 260461) Thisinvention relates to a novel method for the preparation of newphosphates of the structure where R is a radical of the structure R1 R3BH where R is either an alkyl or an aryl radical, R is either hydrogenor an alkyl radical, but R and R can together with the where R is eitheran alkyl or aryl radical, R is either hydrogen or an alkyl radical, butR and R can together with the radical be a cycloalkylidene radical and Xis oxygen or sulfur.

These new compounds can be used to impart fla m e- 5 proofing propertiesLo stypep e-gpaleic modifiedalkyds by replacing a part (up to about 10%)ofthe s'tyrene-orthew can be used as thermosetting molding materialsfor producing shaped plastic artfil es whiiih are il affie'i'esistant.Also, those phosphates of this invention in which X is oxygen are quitesuitable for use as additives in distillate fuels, such as thehydrocarbons of the gasoline boiling range which contain wellknownorgano-rnetallic additives, such as tetraethyl-lead, in which theyfunction as glow suppressants and lead scavengers. Generally, it isdesirable to add the compounds of this invention in an amount sufiicientto provide from about 0.01 to 2.0 mols of phosphorus per mol of metal.Of the new phosphates in which X is sulfur, those wherein R is analkenyl radical'of more than 4 carbon atoms are useful as additives formineral lubricating oils to impart extreme pressure properties theretowhen used in concentrations of at least 0.5% by Weight based upon themineral oil, whereas those having 1-4 carbon atoms have insecticidalactivity towards aphids and other similar insects which attack plants bysucking their juices. For such insecticidal use the compounds of thisinvention can be applied to the foliage of plants as water base sprays,such sprays being prepared in a suitable manner, as by dispersiompf thecompounds inwwater, using conventional emulsifying agents such as thehigher-alkylbenzenesulfonates, with or without the use of a waterimmisciblesolvent, the conf l fi'f i ll 'l 3,079,417 Patented Feb. 26,1963 centration of the active compound being about 1% or less.

The following non-limiting examples will further illustrate thepreparation of our new compounds by the method of this invention. Partsare parts by weight unless otherwise stated.

Example 1 To a suitable reaction vessel capable of withstanding superandsub-atmospheric pressures and having agitation means, means for heatingand cooling its contents, means for the measurement of temperature andpressure and means for the addition and removal of solids and liquids,there is charged 150 cc. of dry benzene, 98 parts of cyclohexanone andparts of pyridine. To the resulting mixture 51 parts of phosphorylchloride is added dropwise over a period of about 45 minutes whilemaintaining the reaction mixture at a temperature of about 25-30 C.After completing the addition of the phosphoryl chloride the mixture isrefluxed for 4 to 8 hours, washed with water and dried. The benzene isremoved by distillation to yield tricyclohexenyl phosphate which boilsat 250 C. at 1 mm. of mercury absolute.

Example 2 To a suitable reaction vessel there is charged cc. of drybenzene, 72 parts of acetophenone and 51. 2 parts of pyridine. To thismixture there is slowly added over a period of about 30 minutes andwhile keeping the reac- Example 0 In a manner similar to the procedureof Example 1, 114 parts of di-n-propyl ketone, 95 parts of pyridine and51 parts of phosphoryl chloride are used to prepare about 26 parts oftriheptenyl phosphate, 'an amber liquid.

Example 4 To a suitable reaction vessel is charged 200 cc. of drytoluene, 116 parts of hexanthione-3, and 200 parts of tributylamine. Tothis mixture there is slowly added while keeping the reaction mixture ata temperature of about 30 C., parts of thiophosphoryl chloride.Thereafter the reaction mixture is refluxed for 4 to 8 hours and wateris added. The resulting phases are separated and the toluene phase iswashed with water and dried. After removal of the toluene bydistillation and fractionation of the material remaining after removalof the toluene, there is recovered about parts of trihexenyltetrathiophospirate.

Generally following the above procedure other phosphates of the typedescribed can be prepared, such as tripropenyl phosphate, tri-butenylphosphate, tri-pentenyl phosphate, tri-hexenyl phosphate, tri-octenylphosphate, tri-decenyl phosphate, tri-cyclopentenyl phosphate,tricyclooctenyl phosphate, tris(l-phenyl-Lpropenyl) phosphate, tris(1phenyl 2 propenyl) phosphate, tris (1- naphthyl vinyl) phosphate,tris(1-phenyl-1-butenyl) phosphate, tris(l-phenyl-Z-heptenyl) phosphate,and the like. In addition to pyridine as the hydrogen chloride acceptorthere can be used other tertiary amines such as triethylamine,quinoline, dimethyl cyclohexylamine, dimethyl aniline, tributylamine orother acceptors which do not interfere-with the reaction, as by reactingwith the POCl or P501 nun iitiiUii Examples of ketones which can be usedin this invention are the aliphatic ketones, e.g. acetone, methyl ethylketone, diethyl ketone, methyl isopropyl ketone, isopropyl sec-butylketone, hexanone-2, hexanone-3, octanone-Z; the cycloaliphatic ketones,e.g. cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone; andthe aryl alkyl ketones, e.g. phenyl propyl ketone, phenyl butyl ketone,phenyl hexyl ketone, phenyl octyl ketone, tolyl ethyl ketone, xylylpropyl ketone, naphthyl propyl ketone.

Other modes of applying the principles of this invention will beapparent to those skilled in the art. Accordingly, while this inventionhas been described by reference to various specific examples andembodiments, it is to be understood that the invention is not limitedthereto and that it can be variously practiced within the scope of thefollowing claims.

What is claimed is:

1. Phosphates represented by the structure wherein R is a radical of thestructure where R is selected from the group consisting of phenyl andnaphthyl radicals, R is selected from the group consisting of hydrogenand alkyl radicals, the sum of the carbon atoms of R and R being up to13, except that R and R together with the radical can be a cycloalkenylradical, and X is selected from the group consisting of oxygen andsulfur.

2. Phosphates of claim 1 where X is sulfur.

3. Phosphates of claim 1 where X is oxygen.

4. Phosphates of claim 1 where R and R together with the radical forms acycloalkenyl radical.

5. Phosphates of claim 3 where R and R together with the radical forms acycloalkenyl radical.

6. Tricyclohexenyl phosphate wherein the double bond is in the a,}?position.

7. Phosphates of claim 1 Where R is a phenyl radical and R is hydrogen.

8. Phosphates of claim 3 where R is a phenyl radical and R is hydrogen.

9. Tri-alpha-styryl phosphate,

10. In a method for producing the phosphates represented by thestructure where R is a radical of the structure where R is selected fromthe group consisting of alkyl, phenyl and naphthyl radicals, R isselected from the group consisting of hydrogen and alkyl radicals, thesum of the carbon atoms of R and R being up to 13, except that R and Rtogether with the radical can be a cycloalkenyl radical, and X isselected from the group consisting of oxygen and sulfur, the stepcomprising reacting in the presence of a tertiary amine a compoundselected from the group consisting of phosphoryl chloride andthiophosphoryl chloride with a ketone 0f the structure X=CCH:

where R R and X have the aforedescribed significance.

11. A method of claim 10 where X is oxygen.

12. A method of claim 10 where X is sulfur.

13. In a method for producing the phosphates of claim 5, the stepcomprising reacting phosphorous oxychloride and an alicyclic mono-ketonem the presence of a tertiary amine.

14. In a method for producing the phosphates of claim 8, the stepcomprising reacting phosphorous oxychloride and a mono-ketone of thestructure References Cited in the file of this patent UNITED STATESPATENTS 2,176,416 Britton et al Oct. 17, 1939 2,546,422 Cross Mar. 27,1951 2,557,805 Upson June 19, 1951 2,574,515 Walter et al Nov. 13, 19512,589,326 Oberright et a1 Mar. 18, 1952 FOREIGN PATENTS 285,038Switzerland Dec. 16, 1952 OTHER REFERENCES Getter et al.: ChemicalAbstracts 52, 295 (1958).

1. PHOSPHATES REPRESENTED BY THE STRUCTURE